Condensation products



- United States Patent 3,166,548 Patented Jan. 19, 1965 CDNDENSATION PRQDUCTS Willard H Kirkpatrick, Sugar Land, and Virgil L. Scale, Houston, Tex., assignors to Naico Chemical Company, a corporation of Delaware No Drawing. Continuation of application I Set. No. 596,816, July '10, 1956. This application Aug. 5, 1960, Ser. No. 47,608

22 Claims. (Cl. 260-97.5)

This invention relates to new and useful condensation products, more particularly condensation products of aliphatic polyamines having at least three amino groups and organic carboxy acids and to a method of producing such condensation products.

One of the objects of the invention is to provide new and useful surface active compositions which are suitable for employment in a wide variety of uses where surface activity is necessary or desirable.

Another object of the invention is to produce surface active compositions which have improved properties as compared with known surface active compositions.

A further object of the invention is to produce new and useful surface active compositions which are less expensive to manufacture than many known surface active materials.

An additional object of the invention is to provide surface active compositions which can be prepared from readily available raw materials.

Another object of the invention is to provide a method for producing compositions of te type previously described. Other objects will appear hereinafter.

These objects are accomplished in accordance with the invention by condensing aliphatic polyamines containing at least three primary and/or secondary amino groups (groups having at least one hydrogen on the amino nitrogens) and an organic carboxy acid, the proportions of the organic carboxy acid being a molar excess within the range from 1% to 40% over a 1:1 molar ratio of carbo-xy (COOH) in the organic carboxy acid to nitrogen (N) in the primary and secondary amine groups of the aliphatic olyamine. The excess acid in many cases probably acts as a plasticizer for the surface active mixture.

.The condensation reaction should be effected under conditions facilitating the elimination of water, preferably at temperatures within the range of 165 C. to 300 C. to produce a water wettable product. The condensation is carried out until about a mole of chemicallycombined water has been eliminated for each mole of amino nitrogen. This excludes, of course, free water present in thereaction mixture as an impurity or diluent. We thus produce a product containing essentially no residual basic 3 amino groups.

The nature and characteristics of the condensation products will vary depending upon the initial reactants.

To a large extent the end products can be described as polyamides but the excess of the organic carboxylic acid employed in the condensation reaction gives the resultant product desirable properties not possessed by condensation products made by condensing the same reactants with anexcess of the amineover the carboxylic acid.

The invention will be further illustrated by the following examples in which the quantities are stated in parts by weight unless otherwise stated.

Example I gradually to 212 C., and the reaction was stopped after 2O cc. of aqueous distillate had been obtained. The product was a liquid.

Example 11 The procedure was the same as'that described in Example I except the quantity of tall oil was increased to 350 parts, the quantity of sulfur dioxide extract was increased to 260 parts, the maximum temperature was 236 C. and the reaction was stopped after 17.5 cc. of aqueous distill-ate had been obtained. The product was aliquid.

Example III The procedure was the same as in Example Iexcept that the quantity of the diethylenetriamine was reduced to 25 parts and the maximum temperature was 232 C. The product was a liquid.

Example IV The condensation reaction was effected by heating to-.

gether 25 parts of die-thylene triamine, 350 parts of tall oil, and 260 parts of sulfur dioxide extract to a maximum temperature of 235 C. and stopping the reaction after 14 parts of aqueous distillate had been obtained. The product was a liquid.

Example V The condensation was effected by heating together 38 parts of tetraethylenepentamine, 300 parts of tall oil and 210 parts of sulfur dioxide extract to a maximum temperature of 215 C. and stoppingthe reaction after 18 parts of aqueous distillate had been obtained. The prodv stopping the reaction after 18 parts of aqueous distillate had been obtained. The product was a liquid.

Example VII I 1 The condensation was effected by heating together 4 parts of dipropylenetriamine, 300 parts of tall oil and I 220 parts of sulfur dioxide extract to a maximum temperature of 230 C. and stopping the reaction after18 r parts of aqueous distillate had been obtained. The prod uct was a liquid. 7 Example VIII The condensation was effected by heating together 49 parts of hydroxyethyldiethylenetriamine, 300 parts of tall oil and 220 parts of sulfur dioxide extract to a maximum temperature of 225 C. and stopping the reaction after 18 parts of aqueous distillate had been obtained. The" product was a liquid.

It is believed that the hydroxyl group in the hydroxyethyldiethylenetriamine remains unreacted.

In the foregoing examples, theweight ratio of acid to amine varies from 5:1 to 14: 1.

In the following examplesthe same general procedures are used as in the preceding examples except that the.

organic carboxylic acid is a dimer acid consisting essentially of dilinoleic acid. 1

Weight Weight Max. Aque- Weight Y- Example Amine Weight 'Dimer Sulfur Temp, ous Dis- Ratio N o. Amine Acid Dioxide C. tillate Acid to Extract amine A 40 300' 215 211 "20. 5. 7. 5 A 30 300 220 212 16 10; B 32 300 220 215 r 16 9.4; 0 34 300 220 215 16 s. s; D 53 300 240 230 20 5. 7: E 39 300 220 225 16 7. 7; F I 49 300 240 220 18 6.1:

The method used in the preparation of the dimer acids is set forth in the Journal of the American Oil Chemists Society, 24,65 (March 1947). acids are as follows:

The specification of these Neutral equivalent 290-310 Iodine value 80-95 Color Gardner 12 maximum Dimer content Approximately 85% Trimerand higher Approximately 12% Monomer Approximately 3% In Examples X to inclusive, the products were all solids. In Example XVI, the product was a liquid.

Weight Weight Max. Aque Weight Example Amine Weight VR-l Sulfur Temp., ous Dis- Ratio No. Amine Acid Dioxide C. tillate' Acid to Extract Amine I The VR1 acid is a mixtureof polybasic acids with an average molecular weightofaboutlOOO. It has an aver-' age of slightly more than two carboxylic acid groups per molecule. It is a by-product acid, and is a dark amber, rather viscous liquid. A typical sample of VR- l acid has the following analysis:

Acid number 150 Iodine number 36 Saponification No. 172 Unsaponifiable matter, percent 3.7; 3.5 Moisture content, percent 0.86

In Examples XXI to XXIII, inclusive, the products were all solids. In Examples XVIII to XX and XXIV, inclusive, the products were liquids. 7

Example XXV The condensation was effected by heating together 37 parts of triethylenetetramine, 250 parts of VR-l acid, 150 parts of dimer acid andf2-8O parts of sulfur dioxide. ex tract to a maximum temperature of 230 C. andstopping the reactionafter 18 parts of aqueous distillate had been obtained. The product was a solid.

Example XXVI The. condensation was effected by heating together 49 parts of hydroxyethyldiethylenetriamine, 166 parts of ferred to herein as a polyalkylene polyamine.

is usually satisfactory. If technical 28% aqueous ammonia is employed, primary, secondary and tertiary amines are obtained invarying proportions, dependent entirely on the alkylene oxide-ammonia ratio. In rectification of the reaction mixture the, various amines are separated by distillation. The tertiary alkylolamine, being the highest boiling member, comes over last. .In commercial operations there is a gradualaccumulation of still bottoms or still residues consisting of materials having boiling points above 280 C. at atmospheric pressures and considerably in excess of the corresponding tertiary alky1. olaniine. constitution of these residues.

The preferred alkylene oxide-ammonia reaction prodnot employed as a starting material is derived from the manufacture of commercial triethanolamine by the reacion of ethylene oxide and ammonia. 'The material is a dark, very viscous, hygroscopic liquid which boils above 244 C. at mm.

The'manufacture of the following primary, secondary and tertiary alkylolamines from alkylene oxides and ammonia results in the formation of still residues which would be suitable for the purpose of the invention: diethanolamine, octylethanolamine, cyclohexylethanolamine, dipropanolamine, propylpropanolamine, benzylethanolamine, propyldiethanolamine, tripropanolamine, methyldipropanolamine, cyclohexyldiethanolamine, ethyldicyclohexanolamine, trihexanolamine, 2-amino-2-methyl-lpropanol, octadecyldiethanolamine, and polyethanolamine.

The amines preferably employed in making condensation'products in accordance with the invention are polyalkylene or hydroxy polyalkylene polyamines containing at least three amino groups. The preferred amines are those in which the. alkylene groups contain either two or three carbon atoms. If the amine contains two terminal primary amino groups and one or moresecondary amino groups interconnected by alkylene chains the amine isre If one or more of the alkylene groups in the polyalkylene poly amines contains a hydroxyl group it is referred to herein.

as a hydroxy polyalkylenepolyamine. If one or more of the nitrogen atoms in the polyalkylene polyamines has attached thereto a hydroxyalkyl' radical it is referred to herein as a hydroxyalkyl or allranol polyalkylene polyamine; The examples illustratethealiphatic polyamines which are most readily availablecommercially at the present time but it will be understood thatJother aliphatic polyamines can be employed.

In the'above examples thepolyarnine H'isfa still residue 7 remaining from the production of'ethylene amines. In

,the manufacture ofleth yle ne amines, ethylene dichloride.

' is reacted with ammonia. Reaction conditions vary but 7 VR-l acid, 200parts of dimer acid and 265 parts of sulfur dioxide extract to a maximum temperature-of 225 C.

andstopping the reaction after. 18 parts of aqueous distil late had been obtained; The product was a solid. 7

Suitable products can be prepared from polyamine T which is a still residue remaining from the reaction of an 7 in all cases a mixture of the members of'the series is obtamed. At comparatively low'temperatures and pressures predominantly ethylene diamineisformed in low yields At higher temperatures and pressures the yields are greaterv and the proportion of' the polyethylene polyamines is higher. In the recovery of the higher polyethylene polyamines by distillation' there remainsastill residue which.

constitutes the polyamine Hconsis'tingof thehomologuesy higher than tetraethylenepentamine. In commercial practice polyamine H is too viscous for handling and 25% of diethylenetriarnine is mixed with it to form an easily handled productbdesignated as Polyamine H Special. Similar still residues fromthe production-of other poly alkylene polyamines would'be suitable for the purpose of 7 crystalline sediment. of'abietic acid. "From'the results of;

several investigators the following principal constituents There is no authentic-information as to the.

of tall oil are indicated: resin acids 30% to 45 fatty acids 45% to 60%, unsaponifiable matter 6% to 12%. The unsaponifiable portion is a yellow viscous oil containing a waxy or pitchy material. The specifications of the particular grade of tall oil which we prefer to use is as follows:

Iodine number 148.83

Thiocyanogen--iodine number 91.1 Percent saturated fatty acids none Percent unsaturated fatty acids 100 Titer test, C. 5.5 Pour test, C 4.4

Cloud test, C. to 12.8

Another organic carboxy acid material which has been used to produce materials satisfactory for the purposes of the invention is a vegetable residue which results from the distillation and acidulation of split soap stock. The ester bodies contained in the material are largely triglycerides. There are small quantities of diand polybasic acids in the product but the exact composition in this regard is not known. An average specification for this type of material is as follows:

Acid value 45 Saponification value 150 Iodine value 100 Color (Bartlett) 13 Viscosity (Zahn G at 75 C.) seconds 15 The material is designated commercially as VR fatty acids.

As examples of organic carboxy acids which have been found to be particularly suitable for the purpose of the invention there may be mentioned linolenic acid, linoleic acid, oleic acid, lauric acid, myristic acid, stearic acid, palmitic acid, other commonly available long chain acyclic acids, and polymeric unsaturated acyclic acids. Of these acids those having a plurality of double bonds (e.g., linolenic and linoleic acids) may also be called drying oil acids. Carbocyclic carboxy acids of the terpene type can also be used as the source of the carboxy acid. These include abietic acid, and related derivatives such as rosin, polymerized rosin, dehydrogenated rosin, and cracked copals.

As illustrations .of organic polycarboxy acids which may be employed in preparing the condensation products there are in addition to the dimer acid and the VR-l acid described in the examples, such acids as adipic acid, suberic acid, azelaic acid and sebacic acid.

The preferred acids can be described as detergent forming acids and contain at least six carbon atoms in the molecule.

The sulfur dioxide extract referred to' in the examples is a lay-product from the Edeleanu process of refining petroleum in which the undesirable fractions are removed by extraction with liquid sulfur dioxide. After removal of thesulfur dioxide .a mixture of hydrocarbons, substantially aromatic in character, remains which is designated in the trade as S0 extract. Examplesof other suitable hydrocarbon vehicles are toluene, xylene, gas, oil, diesel fuel, bunker fuel and coal tar solvents. The above cited examples of solvents are adaptable to azeotropic distillation as would'also be any other solvent which is immiscible with water, miscible with the reacting mass and has a boiling point or boiling range in excess of the boiling point of water.

Especially good results have been obtained in the use of condensation products prepared as described 'in Examples I and XVII.

A list of a few typical uses for the products of the present invention are the following: emulsifying agents, aids in carbonizing; Washing agents, dye assistants; dispersing agents in making emulsions and dispersions of various chemicals, such as emulsions of hydrocarbons of various groups of the aliphatic and aromatic series; terpene emulsions; Wetting compositions in emulsified form; dispersing agents in making emulsified germicides; color lakes; dye preparations, boring oil; drilling oils; emulsions of various animal and vegetable fats and oils; greasing compositions in emulsified form; lubricating compositions containing vegetable or animal fats and oils; solvents for fats in emulsified form; wetting compositions containing oils in emulsified form; wire-drawing oils in emulsified form, printing inks, writ-ing inks; insecticidal preparations in emulsified form; emulsified dressing compositions containing varioussubstances such as shellac, gums, natural and synthetic resins, fats and 'oils; emulsified fat liquoring baths; emulsified finishing compositions, emulsified soaking compositions containing neats-foot oil or other oils to be used as leather fat liquors, emulsified waterproofing compositions; automobile polishes; cleansing compositions containing soaps; compositions for cleansing paint and metal surfaces; degreasing and greasing compositions in emulsified form, detersive and scouring compositions; furniture polishes in emulsified form; metal polishes in emulsified form; scouring compositions for woodwork, linoleum, rugs, and the like; shoe creams and polishes in emulsified form; waterproofing compositions in emulsified form for treating miscellaneous fibrous and other compositions of matter; coating compositions for oilcloth and linoleum; asphaltic paints and varnishes, emulsified paints and varnishes; pigment emulsions; shellac emulsions; emulsified preparations used for the treatment of paper and pulp products; sizing compositions in emulsified form containing rosin, casein, starches and the line; Waxing compositions in emulsified creams in emulsified form, emulsified shampoos; lotions, latherless shaving creams, various emulsified perfumes and cosmetics; emulsions containing petroleum or heavy petroleum distillates; emulsified cutting oils for lathe and screw-press work; kerosene emulsions;

naphtha emulsions; soluble greases in emulsified form; soluble oils in emulsified form, for-lubricating textile machinery, various emulsified textile oils; rubber compositions in emulsified form; special emulsified prepara tions used for coating, projecting, decorating and other surface treating of rubber merchandise; hand-cleansing compositions in emulsified form; various emulsified cleansing and scouring compositions containing soap; dressing compositions in emulsified form; dispersions used for degreasing and washing raw wool; emulsified preparations =for degumming s-ilk; emulsions for soaking silk; emulsified mercerizing baths, special lubricating compositions used in weaving, knitting, warping and winding; emulsions for fire extinguishers; emulsions for the preservation and impregnation ofwood; and emulsions for mo'rdanting. I A

This application is a continuation of our copending application Serial No. 596,816 filed July 10, 1956, now abandoned, which is a continuation-in-part of our application Serial No. 275,014, filed March 5, 1952, now abandoned.

The invention is herebyclaimed as follows:

1. A condensation product with the elimination of water of a compound from the group consisting of hydroxy polyalkylene polyamines and polyalkylene polyamines containing at least three amino groups from the group consisting of primary and secondary amino groups and an organic carboxy detergent-forming acidin which a carboxy group is linked to a hydrocarbon group containing at least six carbon atoms from the class cor sisting of saturated hydrocarbon groups and unsaturated hydrocarbon groups wherein the unsaturation consists of double bonds, the proportions of said organic carboxy acid being a molar excess of at least 1% and not more than 40% over a 1:1 molar ratio of the carboxy groups in the organic car-boxy acid to the amino nitrogens of the polyalkylene polyamine, the amino groups being reacted with said acid to produce a product containing no residual basic amino groups.

2. A condensation product with the elimination of water of a polyalkylene polyamine containing at least three amino groups from the group consisting of primary and secondary amino groups and the alkylene groups therein being selected from the group consisting of ethylene and propylene groups and an organic carboxy detergent-for-ming acid containing one to two carboxy groups linked to a hydrocarbon group containing at least six carbon atoms from the class consisting of saturated hydrocarbon groups and unsaturated hydrocarbon groups wherein the unsaturation consists of double bonds, the proportions of said organic 'carboxy acid being a molar excess within the range from 1% to 40% over a 1:1 molar ratio of carboxy groups in the organic carboxy acid to amino nitrogens of the polyalkylene polyamine, the condensation being efiected at temperatures within the range of 165 C. to 300 C. to produce a product containing no residual basic amino groups.

3. A condensation product with the elimination of water of a polyalkyline polyamine containing at least three amino groups from the group consisting of primary and secondary amino groups and a higher molecular weight, monocarboxylic organic acid consisting of a single carboxy group linked to a hydrocarbon group having at least twelve carbon atoms from the group consisting of satuproduce a product containing no residual .basic: amino groups.

excess Within the range from 1%"t o 40% over a 1:1

molar ratio ofthe carboxy groups in the organic carboxy acid to the amino nitrogens or" the polyalkylene polyo the range of 165 C. to 300 C. to produce a 4. A condensation product with the elimination of carboxy group linked to a hydrocarbon group havingat least twelve carbon atoms from the group consisting of saturated hydrocarbon groups and-unsaturated hydro carbon groups wherein the unsaturation consists of double bonds,v the proportions of said organic carboxy acid being a molar excess within the range from 1% to over 'a-l:l molar ratio of carboxy groups in the organic carboxy acid to amino nitrogens of the polyalkylene polyamine, the condensation being effected at temperatures Within the range of 165 C. to 300 C. to produce a product containing no residual basic amino groups.

5. A condensation product with the elimination of water of a polyalkylene polyamine containing at least three amino groups from the group consisting of primary I and secondary amino groups and'a dicarboxylic organic acid having at least six carbonatom'sbonsisting of two carboxylic groups, linked to an aliphatic. hydrocarbon group from theclass consisting of saturated aliphatic hydrocarbon groups and unsaturated hydrocarbon groups wherein the unsaturation consists of double bonds, the

proportions or said organic carboxy acid being a molar amine,.the amino groups being reacted with said acid to produce a product containing no residual basic amino groups.

6. A condensation product with the elimination of water of a polyalkylene pclyamine containing at least three amino groups from the group consisting of primary and secondary amino groups and the alkyleue groups therein being selected from the group consisting of ethylene and proplene groups, and a dicarboxylic organic acid having at least six carbon atoms consisting of two carboxylic groups linked to an aliphatic hydrocarbon group from the class consisting of saturated aliphatic hydrocarbon groups and unsaturated hydrocarbon groups wherein the unsaturation consists of double bonds, the proportions of said organic carboxy acid being a molar excess within the range from 1% to 40% over a 1:1 molar ratio' of 'carboxy groups in the organic carboxy acid to amino nitrogens of the polyalkylene polyamine, the condensation being effected at temperatures within product containing no residual basic amino groups.

7. A condensation product with the elimination of water of a polyalkylene polyamine containing at least three amino groups from the group consisting of primary and secondary amino groups and tall oil, the proportions of tall oil being a molar excess within the range from 1% to 740% over a 1:1 molar ratio of the carboxy groups in tall oil to the amino ni-trogens of the polyalkylene polyamine, theamino' groups being reactedwith the tall oil to produce a product containing no residual basic amino groups.

8. A condensation product with the elimination of 9. A condensation product with the elimination of 7 water of a polyalkylene polyamine containing at least three amino groups from the group consisting of primary and secondary amino groups and a dimerof linoleic acid,

the proportions of said dimer acid b'eing'a molar excess within the range from 1%to 40% over a 1:1 molar ratio of the carboxy groups in the dimer acid to. the amino nitrogens of the polyalkylene polyarnine, the amino groups being. reacted with said acid to produce a. product con taining no residual basic amino groups. V 10. A condensation product with the elimination of water of a polyalkylene polyamine containing at least three amino groups from the group'consisting of primary and secondary'amino groups and the .alkylene groups therein being selected from the groupconsting of ethylene and propylene groups, and a dimer ofiinoleic acid, the proportions of said dimer acid being a molar excess within the range from 1% to 40% over a 1:1 molar ratio of carboxy groups in said dimer acid to amino 11. A condensation product with the elimination of water of"a polyalkylene polyamine containing at least 7 three amino groups from the group consisting of primary V and secondary amino groups and an organic carboxy acid comprisinga mixture of polybasic organic acids having an average molecular weight of about 1,000 and an average 9 of slightly more than two carboxyl groups per molecule, the proportions of said organic carboxy acid being a molar excess within the range from 1% to 40% over a 1:1 molar ratio of the carboxy groups in the organic carboxy acid to the amino nitrogens of the polyalkylene polyamine, the amino groups being reacted with said acid to produce a product containing no residual basic amino groups.

12. A condensation product with the elimination of water of a polyalkylene polyamine containing at least three amino groups from the group consisting of primary and secondary amino groups and the alkylene groups therein being selected from the group consisting of ethylene and propylene groups, and an organic carboxy acid coprising a mixture of polybasic organic acids having an average molecular weight of about 1,000 and an average of slightly more than two carboxyl groups per molecule, the proportions of said organic carboxy acid being a molar excess within the range from 1% to 40% over a 1:1 molar ratio of carboxy groups in the organic carboxy acid to amino nitrogens of the polyalkylene polyamine, the con densation being effected at temperatures within the range of 165 C. to 300 C. to produce a product containing no basic residual amino groups.

13. The condensation product with the elimination of water of diethylenetriamine and tall oil, the proportions of tall oil being a molar excess of at least 1% and not more than 40% over a 1:1 molar ratio of the carboxy groups in tall oil to the amino nitrogens of diethylenetriamine, the amino groups being reacted with the tall oil acids to produce a product containing no basic amino groups.

14. The condensation product with the elimination of water of diethylenetriamine and an organic carboxy acid comprising a mixture of polybasic organic acids having an average molecular weight of about 1,000 and an average of slightly more than two carboxyl groups per molecule, the proportions of said organic carboxy acid being a molar excess within the range from 1% to 40% over a 1:1 molar ratio of the carboxy groups in the organic carboxy acid to the amino nitrogens of diethylenetriamine, the amino groups being reacted with said acid to produce a product containing no residual basic amino groups.

15. The polymerization condensation reaction product, with the elimination of chemically combined water at temperatures from 165 C. to 300 C., of about 8.6 to 14 parts by weight of tall oil and 1 part by weight of diethylenetriamine.

16. The polymerization condensation reaction product, with the elimination of chemically combined water at temperatures from 165 C. to 300 C., of about 9 parts 10 i by weight of tall oil and 1 part by weight of diethylenetriamine.

17. The polymerization condensation reaction product, with the elimination of chemically combined water at temperatures from 165 C. to 300 C., of 5 to 14 parts by weight of tall oil and 1 part by weight of tetraetnylenepentamine.

18. The polymerization condensation reaction product, with the elimination of chemically combined water resulting from heating to an ultimate temperature of about 212 C., of about 8.6 to 14 parts by weight of tall oil and 1 part by weight of diethylenetriamine.

19. The polymerization condensation reaction product, with the elimination of chemically combined water, of 5.7 to parts by weight of a mixture of polymerized fatty acids comprising principally dicarboxylic acids containing at least 36 carbon atoms per part of a polyethylene polyamine containing 2 to 5 amino groups.

20. The polymerization condensation reaction product of tall oil reacted with a polyalkylene polyamine containing at least three amino groups from the group consisting of primary and secondary amino groups at a temperature from 165 C. to 300 C., the quantity of said tall oil corresponding to in excess of 3 molecular equivalents of tall oil reacted with one molecular equivalent of said polyalkylene polyamine, said excess being a molar excess within the range from 1% to 40% of a 1:1 molar ratio of carboxy groups in tall oil to amino nitrogens of the polyalkylene polyamine.

21. The polymerization condensation reaction product of tall oil reacted with a diethylenetriamine at a temperature from C. to 300 C., the quantity of said tall oil corresponding to in excess of 3 molecular equivalents of tall oil reacted with one molecular equivalent of said diethylenetriamine said excess being a molar excess within the range from 1% to 40% of a 1:1 molar ratio of carboxy groups in tall oil to amino nitrogens of the diethylenetriamine.

22. The polymerization condensation reaction product resulting from heating to an ultimate temperature of about 165 C. to 300 C. a mixture of one molecular equivalent of diethylenetriamine with from 3.46 to 4.94 molecu lar equivalents of tall oil.

References Cited in the file of this patent UNITED STATES PATENTS 2,262,738 De Groote Nov. 11, 1941 2,312,387 Christmann et a1. Mar. 2, 1943 2,366,498 De Groote et al Jan. 2, 1945 2,466,517 Blair et a1. Apr. 5, 1949 2,857,331 Hollingsworth et al Oct. 21, 1958 

1. A CONDENSATION PRODUCT WITH THE ELIMINATION OF WATER OF A COMPOUND FROM THE GROUP CONSISTING OF HYDROXY POLYALKYLENE POLYAMINES AND POLYALKYLENE POLYAMINES CONTAINING AT LEAST THREE AMINO GROUPS FROM THE GROUP CONSISTING OF PRIMARY AND SECONDAY AMINO GROUPS AND AN ORGANIC CARBOXY DETERGENT-FORMING ACID IN WHICH A CARBOXY GROUP IS LINKED TO A HYDROCARBON GROUP CONTAINING AT LEAST SIX CARBON ATOMS FROM THE CLASS CONSISTING OF SATURATED HYDROCARBON GROUPS AND UNSATURATED HYDROCARBON GROUPS WHEREIN THE UNSATURATION CONSISTS OF DOUBLE BONDS, THE PROPORTIONS OF SAID ORGANIC CARBOXY ACID BEING A MOLAR EXCESS OF AT LEAST 1% AND NOT MORE THAN 40% OVER A 1:1 MOLAR RATION OF THE CARBOXY GROUPS IN THE ORGANIC CARBOXY ACID TO THE AMINO NITROGENS OF THE POLYALKYLENE POLYAMINE, THE AMINO GROUPS BEING REACTED WITH SAID ACID TO PRODUCE A PRODUCT CONTAINING NO RESIDUAL BASIC AMINO GROUPS.
 8. A CONDENSATION PRODUCT WITH THE ELIMINATION OF WATER OF A POLYALKYLENE POLYAMINE CONTAINING AT LEAST THREE AMINO GROUPS FROM THE GROUP CONSISTING OF PRIMARY AND SECONDARY AMINO GROUPS AND THE ALKYLENE GROUPS THEREIN BEING SELECTED FROM THE GROUP CONSISTING OF ETHYLENE AND PROPYLENE GROUPS, AND TALL OIL, THE PROPORTIONS OF TALL OIL BEING A MOLAR EXCESS WITHIN THE RANGE FROM 1% TO 40% OF A 1:1 MOLAR RATIO OF CARBOXY GROUPS IN TALL OIL TO AMINO NITROGENS OF THE POLYALKYLENE POLYAMINE, THE CONDENSATION BEING EFFECTED AT TEMPERATURE WITHIN THE RANGE OF 165*C. TO 300*C. TO PRODUCE A PRODUCT CONTAINING NO RESIDUAL BASIC AMINO GROUPS.
 9. A CONDENSATION PRODUCT WITH THE ELIMINATION OF WATER OF A POLYALKYLENE POLYAMINE CONTAINING AT LEAST THREE AMINO GROUPS FROM THE GROUP CONSISTING OF PRIMARY AND SECONDARY AMINO GROUPS AND A DIMER OF LINOLEIC ACID, THE PROPORTIONS OF SAID DIMER ACID BEING A MOLAR EXCESS WITHIN THE RANGE FROM 1% TO 40% OVER A 1:1 MOLAR RATIO OF THE CARBOXY GROUPS IN THE MINER ACID TO THE AMINO NITROGENS OF THE POLYALKYLENE POLYAMINE, THE AMINO GROUPS BEING REACTED WITH SAID ACID TO PRODUCE A PRODUCT CONTAINING NO RESIDUAL BASIC AMINO GROUPS. 